US4847420A - New hydroxy-thia-alkenes, and processes for their preparation and use - Google Patents
New hydroxy-thia-alkenes, and processes for their preparation and use Download PDFInfo
- Publication number
- US4847420A US4847420A US07/088,810 US8881087A US4847420A US 4847420 A US4847420 A US 4847420A US 8881087 A US8881087 A US 8881087A US 4847420 A US4847420 A US 4847420A
- Authority
- US
- United States
- Prior art keywords
- alcohol
- process according
- mercapto
- diene
- butadiene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
Definitions
- the present invention relates to a new type of hydroxy-thia-alkene, that is aliphatic alcohol-thioethers, having a chain which comprises one or more double bonds. These compounds are useful in the manufacture of polymeric products having unsaturated thioether units or sidechains. Unsaturated polymers having thioether units on their chain are of particular interest in the manufacture of polysulphides intended for the preparation of mastics, jointing compounds and the like. A process of preparation of the aliphatic alcohol thioether compounds also forms part of the invention.
- Alcohol-thioethers having a double bond at the end of the chain of the general form HO--CH 2 --CH 2 --S--PCH ⁇ CH 2 l, in which P is an alkylene group comprising 4 to 6 carbon atoms, particularly 1-hydroxy-3-thia-nonene-8, HO(CH 2 ) 2 --S--(CH 2 ) 4 --CH ⁇ CH 2 , are known and used.
- P is an alkylene group comprising 4 to 6 carbon atoms, particularly 1-hydroxy-3-thia-nonene-8, HO(CH 2 ) 2 --S--(CH 2 ) 4 --CH ⁇ CH 2
- the preparation of this compound requires the use of hexadiane-1,5 and mercapto-ethanol to effect the reaction ##STR2##
- Hexadiene-1,5 is a relatively expensive hydrocarbon and the above reaction takes place with a yield of unsaturated product, which, in practice, does not exceed 80%.
- the present invention provides a substantial advance in the art mentioned above. It achieves the synthesis of a new type of unsaturated alcohol-thioether, the yield of unsaturated products of which is much improved.
- the preparation of these products is practically quantitative and allows the use of starting materials which are much more accessible than those used in the prior art. This improved process allows the preparation of compounds having a chain which can comprise a plurality of double bonds.
- the invention is based upon the quite astonishing discovery that conjugated dienes react with mercapto-alcohols with higher yields of unsaturated products than when using non-conjugated dienes.
- hexadiene-2,4 combines with mercaptoethanol with a yield of unsaturated products well exceeding prior art yield using hexadiene-1,5.
- a mercapto-alcohol is reacted with a conjugated diene in the presence of a free radical catalyst to produce alcohol; thioethers.
- dienes used according to the invention correspond to the formula ##STR3## where R 1 R 4 are aliphatic groups, the same or different, and/or hydrogen atoms.
- the simplest compound, but also the most economical, is butadiene, that is the diene in which all the symbols R 1 to R 4 represent hydrogen atoms.
- Another very interesting diene is isoprene, namely 2-methyl-butadiene-1,3, in which R 1 , R 2 and R 4 are H, while R 3 is methyl; the branching constituted by this can make advantageous modifications to the properties of the products made from the corresponding alcohol-thioethers.
- dienes suitable for carrying out the invention include but are not limited to piperylene, namely pentadiene-1,3, 2-ethyl-butadiene-1,3, hexadiene1,3 or 2,4-octadiene-1,3 or 3,5, limonene etc.
- mercapto-alcohols are suitable for carrying out the invention. To simplify, they are designated here by the general formula HO--A--SH, where A is a branched or unbranched aliphatic chain which may be substituted or unsubstituted, and preferably is comprised of about 1-12 carbon atoms.
- Useful mercaptoalcohols include but are not limited to straight-chain compounds ranging from mercapto-methanol to a mercaptolauryl alcohol. Certain preferred species include the mercapto-ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, alcohols, etc.
- Free radical catalysts are well known and only some of them are mentioned here: azo-bisisobutyronitrile, benzoyl-peroxide, tert.butylperbernzoate, lauroyl-peroxide, isobutyryl peroxide, tert.butyl-peroxyacetate, di-cumyl-peroxide, paramethane-hydroxyperoxide. Photochemical techniques can also be used.
- the temperature at which the diene combines most advantageously with the mercapto-alcohol depends upon the nature of the reactants and that of the catalysts employed. It is generally in the range from 0° to 100° C. and preferably from 50° to 90° C.
- the reactant temperature selected should of course be lower than the temperature of decomposition of the catalyst or any of the reactants.
- molar proportion of the diene used with respect to the mercapto-alcohol is important factor in the new process. It appears in practice that depending upon the molar ratio of diene to mercapto-alcohol, a range of unsaturated alcohol-thioethers can be obtained, where the chain comprises the residue of one or several molecules of the diene per molecule of mercapto-alcohol. This is one of the surprising characteristics of the invention, which produces a very interesting result, in that it becomes possible to prepare useful mixtures of unsaturated compounds. For difunctional compounds, compositions of different unsaturated alcohol-thioethers can thus be synthesized as indicated below. Preferably molar ratios of diene to mercapto-alcohol range from about 1:1 to about 10:1, the preferred ratios being from about 1.5:1 to 6:1.
- A is a branched or unbranched aliphatic chain which may be substituted or unsubstituted, and most preferably contains from 2-6 carbon atoms;
- R 1 , R 3 and R 4 may be the same or different, and are aliphatic groups and/or hydrogen atoms;
- R 2 may be an aliphatic group, hydrogen, an alkylene or a bond and the CH 2 R 2 moiety may be divalent and capable of bonding an additional beta-unsaturated aliphatic chain;
- p gives the degree of polymerization of the beta-unsaturated aliphatic chain and preferably is not less than 2. This coefficient tends to vary with the diene-mercapto-alcohol ratio mentioned above.
- R 3 and R 4 are both hydrogen and R 2 is either hydrogen or a straight-chain alkyl group of from 1 to 6 carbon atoms. It is preferred that R 1 be a moiety having less than 6 carbon atoms (especially less than 5), depending on the nature of the diene used.
- a third series of unsaturated alcohol-thioethers forms in the reaction according to the invention, particularly when there are more than 3 moles of butadiene per mole of mercapto-ethanol. These are products containing more than 2 double bonds for instance: ##STR7##
- This triene or its isomers form in increasing proportions when the butadiene/mercapto-ethanol ratio increases, particularly above 3.
- HTH, HTU and HTP can be separated after distillation of mixtures with their isomers. This can be carried out particularly under the following conditions:
- This variety of structure of the alcohol-thioethers which can be obtained according to the invention allows variation in the properties of the products of use of these compounds.
- the invention provides modification of the diene/mercapto-alcohol molar ratio and, if required, separation of the products obtained, as mentioned above, although use of the crude products constitutes an interesting embodiment.
- reaction mixture composed of:
- the yield with respect to the mercapto-ethanol is practically quantitative.
- the reaction mixture obtained contains about 9 unsaturated functions an 6.6 alcohol functions per kg of product, confirmed by NMR analyses and chemical analysis. These unsaturated functions are totally reactive vis-a-vis compounds with a mercaptan function.
- the reaction mixture obtained contains about 10.2 unsaturated functions and 6.8 alcohol functions per kg of product.
- Example 1 The operations of Example 1 are repeated, but the butadiene is replaced with the same number of moles of hexadiene-1,5.
- the 1-hydroxy-3-thia-nonene-8 (designated by the initials HTN in the following part of the description) is principally obtained. But the yield with respect to the mercapto-ethanol is only 80%.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8414665 | 1984-09-25 | ||
FR8414665A FR2570697B1 (fr) | 1984-09-25 | 1984-09-25 | Nouveaux hydroxy-thia alcenes, leur procede de preparation et applications |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06779506 Continuation-In-Part | 1985-09-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
US4847420A true US4847420A (en) | 1989-07-11 |
Family
ID=9308019
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/088,810 Expired - Lifetime US4847420A (en) | 1984-09-25 | 1987-08-24 | New hydroxy-thia-alkenes, and processes for their preparation and use |
Country Status (21)
Country | Link |
---|---|
US (1) | US4847420A (fr) |
EP (1) | EP0176438B1 (fr) |
JP (1) | JPS6185357A (fr) |
KR (1) | KR890005347B1 (fr) |
AU (1) | AU584123B2 (fr) |
BE (1) | BE903248A (fr) |
BR (1) | BR8504677A (fr) |
CA (1) | CA1250597A (fr) |
DE (2) | DE3561058D1 (fr) |
DK (1) | DK434685A (fr) |
ES (1) | ES8604871A1 (fr) |
FI (1) | FI853651L (fr) |
FR (1) | FR2570697B1 (fr) |
GR (1) | GR852340B (fr) |
HU (1) | HU203871B (fr) |
IT (1) | IT1201471B (fr) |
LU (1) | LU86091A1 (fr) |
NO (1) | NO161913C (fr) |
NZ (1) | NZ213608A (fr) |
PT (1) | PT81194B (fr) |
ZA (1) | ZA857381B (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5118857A (en) * | 1990-07-09 | 1992-06-02 | Phillips Petroleum Company | Polar solvent treatment of n-dodecyl mercaptoethanol |
US20060288949A1 (en) * | 2005-04-12 | 2006-12-28 | Hyperion Innovations, Inc. | Portable Heated padding for pets |
US20060289421A1 (en) * | 2005-04-12 | 2006-12-28 | Hyperion Innovations, Inc. | Portable heated seating |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5145996A (en) * | 1989-11-30 | 1992-09-08 | Ciba-Geigy Corporation | Heteroatom containing perfluoroalkyl terminated neopentyl mercapto-alcohols and compositions therefrom |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB441457A (en) * | 1934-04-16 | 1936-01-20 | Du Pont | Organic condensation products and their manufacture |
US3591475A (en) * | 1968-12-09 | 1971-07-06 | Exxon Research Engineering Co | Preparation of unsymmetrical thiol-allene diadducts |
US3708543A (en) * | 1971-08-09 | 1973-01-02 | Dow Chemical Co | Allyl acetal derivative of 1-halo-3-mercapto-2-propanol |
US3729518A (en) * | 1969-09-25 | 1973-04-24 | Henkel & Cie Gmbh | Novel thia-alkanols |
US3763116A (en) * | 1968-04-10 | 1973-10-02 | Ciba Geigy Corp | Perfluoroalkyl thioether alcohols esters and polymers |
US4086278A (en) * | 1976-03-15 | 1978-04-25 | Ortho Pharmaceutical Corporation | 1-alkenyl thioethers |
-
1984
- 1984-09-25 FR FR8414665A patent/FR2570697B1/fr not_active Expired
-
1985
- 1985-09-17 BE BE2/60793A patent/BE903248A/fr not_active IP Right Cessation
- 1985-09-19 DE DE8585401826T patent/DE3561058D1/de not_active Expired
- 1985-09-19 EP EP85401826A patent/EP0176438B1/fr not_active Expired
- 1985-09-19 DE DE198585401826T patent/DE176438T1/de active Pending
- 1985-09-23 FI FI853651A patent/FI853651L/fi not_active Application Discontinuation
- 1985-09-23 NO NO853721A patent/NO161913C/no unknown
- 1985-09-24 ES ES547250A patent/ES8604871A1/es not_active Expired
- 1985-09-24 CA CA000491438A patent/CA1250597A/fr not_active Expired
- 1985-09-24 JP JP60209039A patent/JPS6185357A/ja active Granted
- 1985-09-24 AU AU47828/85A patent/AU584123B2/en not_active Ceased
- 1985-09-24 IT IT22259/85A patent/IT1201471B/it active
- 1985-09-24 BR BR8504677A patent/BR8504677A/pt unknown
- 1985-09-24 HU HU853594A patent/HU203871B/hu not_active IP Right Cessation
- 1985-09-24 LU LU86091A patent/LU86091A1/fr unknown
- 1985-09-25 KR KR1019850007032A patent/KR890005347B1/ko not_active IP Right Cessation
- 1985-09-25 ZA ZA857381A patent/ZA857381B/xx unknown
- 1985-09-25 GR GR852340A patent/GR852340B/el unknown
- 1985-09-25 NZ NZ213608A patent/NZ213608A/xx unknown
- 1985-09-25 PT PT81194A patent/PT81194B/pt not_active IP Right Cessation
- 1985-09-25 DK DK434685A patent/DK434685A/da not_active Application Discontinuation
-
1987
- 1987-08-24 US US07/088,810 patent/US4847420A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB441457A (en) * | 1934-04-16 | 1936-01-20 | Du Pont | Organic condensation products and their manufacture |
US3763116A (en) * | 1968-04-10 | 1973-10-02 | Ciba Geigy Corp | Perfluoroalkyl thioether alcohols esters and polymers |
US3591475A (en) * | 1968-12-09 | 1971-07-06 | Exxon Research Engineering Co | Preparation of unsymmetrical thiol-allene diadducts |
US3729518A (en) * | 1969-09-25 | 1973-04-24 | Henkel & Cie Gmbh | Novel thia-alkanols |
US3708543A (en) * | 1971-08-09 | 1973-01-02 | Dow Chemical Co | Allyl acetal derivative of 1-halo-3-mercapto-2-propanol |
US4086278A (en) * | 1976-03-15 | 1978-04-25 | Ortho Pharmaceutical Corporation | 1-alkenyl thioethers |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5118857A (en) * | 1990-07-09 | 1992-06-02 | Phillips Petroleum Company | Polar solvent treatment of n-dodecyl mercaptoethanol |
US20060288949A1 (en) * | 2005-04-12 | 2006-12-28 | Hyperion Innovations, Inc. | Portable Heated padding for pets |
US20060289421A1 (en) * | 2005-04-12 | 2006-12-28 | Hyperion Innovations, Inc. | Portable heated seating |
US20070013213A1 (en) * | 2005-04-12 | 2007-01-18 | Hyperion Innovations, Inc. | Portable heated seating |
Also Published As
Publication number | Publication date |
---|---|
AU4782885A (en) | 1986-04-24 |
IT1201471B (it) | 1989-02-02 |
GR852340B (fr) | 1986-01-14 |
NO853721L (no) | 1986-03-26 |
DE3561058D1 (en) | 1988-01-07 |
NO161913C (no) | 1989-10-11 |
ES8604871A1 (es) | 1986-03-16 |
NZ213608A (en) | 1988-06-30 |
FI853651A0 (fi) | 1985-09-23 |
IT8522259A0 (it) | 1985-09-24 |
KR860002462A (ko) | 1986-04-26 |
HUT39424A (en) | 1986-09-29 |
BR8504677A (pt) | 1986-07-22 |
BE903248A (fr) | 1986-03-17 |
EP0176438A1 (fr) | 1986-04-02 |
DK434685A (da) | 1986-03-26 |
DK434685D0 (da) | 1985-09-25 |
FR2570697A1 (fr) | 1986-03-28 |
JPS6185357A (ja) | 1986-04-30 |
ES547250A0 (es) | 1986-03-16 |
DE176438T1 (de) | 1986-09-25 |
FI853651L (fi) | 1986-03-26 |
FR2570697B1 (fr) | 1987-12-04 |
PT81194A (fr) | 1985-10-01 |
HU203871B (en) | 1991-10-28 |
JPH0473426B2 (fr) | 1992-11-20 |
LU86091A1 (fr) | 1986-03-11 |
EP0176438B1 (fr) | 1987-11-25 |
CA1250597A (fr) | 1989-02-28 |
AU584123B2 (en) | 1989-05-18 |
NO161913B (no) | 1989-07-03 |
KR890005347B1 (ko) | 1989-12-23 |
ZA857381B (en) | 1986-05-28 |
PT81194B (pt) | 1988-01-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4163832A (en) | Polythioethers formed by anionic ring opening of episulfides | |
AU600330B2 (en) | Melt processable optically anisotropic polymers | |
EP0176086B1 (fr) | Organocyclosiloxane | |
DE69011362T2 (de) | Hydroxyphenylgruppen enthaltende Siloxan-Verbindungen. | |
US4847420A (en) | New hydroxy-thia-alkenes, and processes for their preparation and use | |
US5571907A (en) | Epoxy monomers from sucrose | |
US3392182A (en) | Novel organosilicon compounds and process for their preparation | |
US3403187A (en) | Polythioetherdithiols and process for producing same | |
US4766195A (en) | Polymers of unsaturated alcohol thioethers | |
EP0150055B1 (fr) | Trifluoro oxétanes substitués et leur préparation | |
US4661645A (en) | Synthesis of styrenated hydroquinone | |
US4012403A (en) | Synthesis of mercapto-substituted silicon compounds | |
US5041594A (en) | Process for preparing organo(poly)siloxanes having Si-linked, conjugated dienyl groups | |
US3506723A (en) | 1-hydroxymethyl-2-hydroxyethyl-cyclopentane | |
US2768212A (en) | Addition of acetals and ketals to olefins | |
US3391209A (en) | Di(omega-alkenyl) methylcyclopentanes | |
US4997988A (en) | Oxa-organic sulfur compounds, their preparation and use | |
EP0065289B1 (fr) | Procédé de synthèse du trialcoyl-tris (3,5-dialcoyl-4-hydroxybenzyl)-benzène | |
US2140713A (en) | Addition products of acetylene and alcohol and process of producing them | |
US3351683A (en) | Production of phosphite esters | |
US4231970A (en) | Reaction products of unsaturated hydrocarbons with P4 S10 and PSX3 | |
US4540526A (en) | Reaction products of unsaturated hydrocarbons with P4 S10 and PSX3 | |
US4496758A (en) | Process for the metathesis of alkenyl esters | |
US4328169A (en) | Process for the preparation of vinylcyclopropane derivatives | |
US5264631A (en) | Process for the preparation of unsymmetrical alkyl trisulfides and products |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: SOCIETE NATIONALE ELF AQUITAINE, TOUR ELF, 2 PLACE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:LABAT, YVES;REEL/FRAME:004782/0765 Effective date: 19871103 Owner name: SOCIETE NATIONALE ELF AQUITAINE, TOUR ELF, 2 PLACE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:LABAT, YVES;REEL/FRAME:004782/0765 Effective date: 19871103 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
FPAY | Fee payment |
Year of fee payment: 12 |